US20100016491A1 - Novel polyolefin resin composition and molded resin obtained therefrom - Google Patents

Novel polyolefin resin composition and molded resin obtained therefrom Download PDF

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Publication number
US20100016491A1
US20100016491A1 US12/513,199 US51319909A US2010016491A1 US 20100016491 A1 US20100016491 A1 US 20100016491A1 US 51319909 A US51319909 A US 51319909A US 2010016491 A1 US2010016491 A1 US 2010016491A1
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Prior art keywords
polyolefin
based resin
component
acid
hydrotalcite
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Sukehiro Niga
Masahide Ishikawa
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New Japan Chemical Co Ltd
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New Japan Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a novel polyolefin-based resin composition and a method for producing the same; a polyolefin-based resin molded article obtained by molding the polyolefin-based resin composition; a method for improving the transparency of a polyolefin-based resin; a method for improving the rigidity of a polyolefin-based resin; and a nucleating agent composition for a polyolefin-based resin.
  • Polyolefin-based resins are used in various fields as materials for film molding, sheet molding, blow molding, injection molding, etc., owing to their excellent moldability, mechanical and electrical properties, etc. With such excellent physical properties, however, polyolefin-based resins have the problems of being generally low in transparency, crystallinity, and rigidity. In order to overcome such problems, techniques using amide-based compounds and the like as nucleating-agent compositions have been proposed (Patent Documents 1 to 4).
  • Polyolefin-based resin compositions containing such amide-based compounds have high crystallization rates. Therefore, injection molding of these compositions contributes to shortened molding cycle time.
  • the molded articles thus obtained also have improved transparency and mechanical properties (e.g., rigidity).
  • Patent Documents-5 and 6 In order to further improve mechanical properties, it is known to add a filler such as talc or the like to a polyolefin-based resin composition containing an amide-based compound.
  • the amount of such filler is generally as large as 5 to 30 weight % based on the polyolefin-based resin.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 1994-192496
  • Patent Document 2 Japanese Unexamined Patent Publication No. 1995-242610
  • Patent Document 3 Japanese Unexamined Patent Publication No. 1995-278374
  • Patent Document 4 Japanese Unexamined Patent Publication No. 1996-100088
  • Patent Document 5 International Publication No. 05/37770 pamphlet
  • Patent Document 6 International Publication No. 05/63874 pamphlet
  • An object of the present invention is to provide a polyolefin-based resin composition capable of yielding a molded article having excellent crystallinity, rigidity, transparency and the like, and a method for producing the same.
  • Another object of the present invention is to provide a polyolefin-based resin molded article having excellent crystallinity, rigidity, transparency and the like obtained by molding the polyolefin-based resin composition; a method for improving the transparency of a polyolefin-based resin; a method for improving the rigidity of a polyolefin-based resin; and a nucleating-agent composition for a polyolefin-based resin.
  • a polyolefin-based resin composition comprising:
  • k is an integer of 3 or 4;
  • R 1 is a residue obtained by removing all of the carboxyl groups from 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid or 1,3,5-benzenetricarboxylic acid;
  • R 2 s are the same or different, and each independently represents a hydrogen atom or a C 1-10 linear or branched alkyl group
  • k is an integer of 3 or 4,
  • R 1 is a residue obtained by removing all of the carboxyl groups from 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid or 1,3,5-benzenetricarboxylic acid;
  • R 2 s are the same or different, and each independently represents a hydrogen atom or a C 1-10 linear or branched alkyl group
  • k is an integer of 3 or 4,
  • R 1 is a residue obtained by removing all of the carboxyl groups from 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid or 1,3,5-benzenetricarboxylic acid;
  • R 2 s are the same or different, and each independently represents a hydrogen atom or a C 1-10 linear or branched alkyl group, and
  • k is an integer of 3 or 4
  • R 1 is a residue obtained by removing all of the carboxyl groups from 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid or 1,3,5-benzenetricarboxylic acid;
  • the method comprising dissolving component (A) completely in a melt of the polyolefin-based resin.
  • a nucleating agent composition (having a uniform composition) for polyolefin-based resins, comprising:
  • k is an integer of 3 or 4,
  • R 1 is a residue obtained by removing all of the carboxyl groups from 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid or 1,3,5-benzenetricarboxylic acid;
  • R 2 s are the same or different, and each independently represents a hydrogen atom or a C 1-10 linear or branched alkyl group, and
  • a polyolefin-based resin composition comprising a polyolefin-based resin, component (A) and component (B), and molding such polyolefin-based resin composition gives a polyolefin-based resin molded article exhibiting excellent crystallinity, rigidity, transparency and heat resistance.
  • nucleating agent composition comprising component (A) and component (B).
  • the nucleating agent composition of the present invention comprising component (A) and component (B) is in the form of a powder with good flowability, and is excellent in transferability through piping, and improves operation efficiency.
  • Component (A) in accordance with the invention is at least one of amide-based compounds represented by general formula (1) shown above.
  • Specific examples of such amide-based compounds include the following compounds:
  • amide-based compounds of general formula (I) in which R 1 is a residue obtained by removing all of the carboxyl groups from 1,2,3-propanetricarboxylic acid or 1,3,5-benzenetricarboxylic acid are preferable. Specific examples are as follows:
  • amide-based compounds may be used alone or at least two of them may be used in suitable combinations.
  • the crystal form of the amide-based compound of the invention is not limited so long as the effects of the invention can be attained; any crystal forms, such as hexagonal, monoclinic, cubic, etc., can be used. Such crystals are known or may be prepared by a known method.
  • the amide-based compound of the invention preferably has a purity of substantially 100%, but may also include small amounts of impurities.
  • the amide-based compound When containing impurities, the amide-based compound preferably has a purity of 90 wt % or more, more preferably 95 wt % or more, and particularly 97 wt % or more.
  • impurities include monoamidedicarboxylic acids and esters thereof, diamidemonocarboxylic acids and esters thereof, which are derived from reaction intermediates or unreacted reactants; imide compounds derived from by-products; etc.
  • the method for producing the amide-based compound of the invention is not limited so long as the desired amide-based compound can be obtained.
  • the amide-based compounds may be produced from specific polycarboxylic acid component(s) and specific alicyclic monoamine component(s) according to a known method (see, for example, Japanese Unexamined Patent Publication No. 1995-242610).
  • aliphatic polycarboxylic acid components include 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,3,5-benzenetricarboxylic acid, derivatives thereof such as acid chlorides and anhydrides thereof; esters of such polycarboxylic acids with C 1-4 lower alcohols, etc.
  • One of such aliphatic polycarboxylic acid components or at least two of them may be subjected to amidation.
  • the alicyclic monoamine components is at least one member selected from the group consisting of cyclohexylamine and C 1-10 (preferably C 1-4 ) linear or branched alkyl-substituted cyclohexylamines.
  • One of such alicyclic monoamine components or at least two of them may be subjected to the amidation.
  • cyclohexylamine 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 2-isopropylcyclohexylamine, 2-n-butylcyclohexylamine, 2-isobutylcyclohexylamine, 2-sec-butylcyclohexylamine, 2-tert-butylcyclohexylamine, 2-n-hexylcyclohexylamine, 2-n-octylcyclohexylamine, 2-n-decylcyclohexylamine, 4-n-propylcyclohexylamine, 4-isopropylcyclohexylamine, 4-n-butylcyclohexylamine,
  • cyclohexylamine Preferable are cyclohexylamine, 2 methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 2-isopropylcyclohexylamine, 2-n-butylcyclohexylamine, 2-isobutylcyclohexylamine, 2-sec-butylcyclohexylamine, 2-tert-butylcyclohexylamine, etc.
  • the alkyl-substituted cyclohexylamine may be a cis isomer, trans isomer, or a mixture of these stereoisomers.
  • the ratio of cis isomer:trans isomer is preferably from 50:50 to 0:100, and more preferably from 35:65 to 0:100, in terms of GLC area %.
  • GLC means gas-liquid chromatography.
  • the particle size of the amide-based compound of the invention is not limited so long as the effects of the invention can be attained; however, the particle size is preferably as small as possible from the standpoint of the dissolving rate (or dissolving time) at which the amide-based compound dissolves in a molten polyolefin-based resin.
  • the maximum particle size of the amide-based compound is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, and particularly preferably 10 ⁇ m or less, as measured by a laser diffraction light scattering method (Volume Standard).
  • Examples of methods for controlling the maximum particle size within the above ranges include a method comprising pulverizing the amide-based compound using a pulverization apparatus known in the art, and a known classifier may be used as required.
  • the pulverization apparatus include Fluidized Bed Counter Jet Mill 100 AFG (product name, manufactured by Hosokawa Micron Corporation), Supersonic Jet Mill PJM-100 (product name, manufactured by Nippon Pneumatic MFG, Co., Ltd.), pin mills, etc.; and examples of classifiers include sieve classifier, dry classifiers (cyclone, micron separators, etc.), and so forth.
  • Component (B) Inorganic Compound
  • Component (B) of the invention is at least one inorganic compound selected from the group consisting of hydrotalcite, calcined hydrotalcite, talc, alkali aluminum double hydroxides, magnesium hydroxide, magnesium oxide, calcium carbonate, and calcium oxide.
  • the hydrotalcite for use in the invention may be a product that is generally commercially available, so long as the effects of the invention are not impaired.
  • hydrotalcites include Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O (manufactured by Kyowa Chemical Industry Co., Ltd., product name “DHT-4A”) Mg 4.5 Al 2 (OH) 13 CO 3 (manufactured by Kyowa Chemical Industry Co., Ltd., product name “DHT-4A2”); Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O (manufactured by Kyowa Chemical Industry Co., Ltd., product name “DHT-6”); and the like.
  • Some of the commercially available products are surface-treated as will be described blow, but represented by the same chemical formula expression as non-surface-treated products.
  • the calcined hydrotalcite is an inorganic oxide obtained by calcining the aforementioned hydrotalcite according to a known process (see JP-A-2006-511679, JP-A-2000-212272, JP-A-4-505449, etc.).
  • the calcined hydrotalcite may be a product that is generally commercially available, so long as the effects of the invention are not impaired.
  • Mg 0.7 Al 0.3 O 1.15 manufactured by Kyowa Chemical Industry Co., Ltd., product name “KYOWAAD 2100” may be mentioned.
  • Talc is synonymous with the compound typically represented by Mg 3 Si 4 O 10 (OH) 2 or the compound referred to as hydrated magnesium silicate.
  • the talc for use in the invention may be a product that is generally commercially available, so long as the effects of the invention are not impaired.
  • “Micro Ace P-6” product name, manufactured by Nippon Talc Co., Ltd.
  • Some kinds of talc may contain small amounts of impurities, such as carbonic acid and other minerals, depending on its origin, but may be used without restriction, so long as the effects of the invention are not impaired.
  • the alkali aluminum double hydroxide for use in the invention may be a synthesized product or a generally commercially available product, so long as the effects of the invention are not impaired.
  • the term “alkali” denotes alkali metals and alkaline earth metals, and examples are lithium, sodium, potassium or other alkali metals, calcium, strontium, barium or other alkaline earth metals. Examples of commercially available products are Li 2 Al 4 (OH) 12 CO 3 .3H 2 O (manufactured by Mizusawa Industrial Chemicals, Ltd., product name, “Mizukalac L”) may be mentioned.
  • the alkali aluminum double hydroxide also includes alkali aluminum double hydroxide carbonates (see for example JP-A-10-45411), hydrocalumite, hydrocalumite carbonates (see for example JP-A-9-241019), etc.
  • the magnesium hydroxide, magnesium oxide, calcium carbonate and calcium oxide for use in the invention may each be a product or reagent that is generally commercially available, so long as the effects of the invention are not impaired.
  • commercially available magnesium hydroxide “Magsarat F” (product name, manufactured by Kyowa Chemical Industry Co., Ltd.) may be mentioned.
  • the aforementioned inorganic compound may be surface treated (by, e.g., a treatment method such as coating) with stearic acid, oleic acid or other higher fatty acids, stearamide, oleamide or other higher fatty acid amides, etc.
  • the pH of the inorganic compound is preferably 7.0 to 14.0, more preferably 7.2 to 13.0, and still more preferably 7.5 to 12.0.
  • the pH value is measured by the method that is described in Examples to be given later.
  • the particle size of the inorganic compound is not limited so long as the effects of the invention are not impaired; however, it is preferably as small as possible from the standpoint of dispersion in molten polyolefin-based resin and refractive index.
  • the particle size of the inorganic compound is preferably such that the median diameter is 50 ⁇ m or less, more preferably 10 ⁇ m, and most preferably 1 ⁇ m, as measured by a laser diffraction light scattering method.
  • polyolefin-based resin of the invention examples include polyethylene-based resins, polypropylene-based resins, polymethylpentene-based resins, polybutene-based resins, etc.
  • high-density polyethylenes examples include high-density polyethylenes, medium-density polyethylenes, linear polyethylenes, ethylene copolymers with an ethylene content of 50 wt % or more (preferably 70 wt % or more), propylene homopolymers, propylene copolymers with a propylene content of 50 wt % or more (preferably 70 wt % or more), butane homopolymers, butene copolymers with a butane content of 50 wt % or more (preferably 70 wt % or more), methylpentene homopolymers, methylpentene copolymers with a methylpentene content of 50 wt % or more (preferably 70 wt % or more), polybutadiene, etc.
  • Such copolymers may be random copolymers or block copolymers. When such resins have stereoregularity, they may be isotactic or syndiotactic.
  • comonomers which can form the copolymers as mentioned above include ethylene, propylene, butene, pentene, hexene, heptene, octane, nonene, decene, undecene, dodecene and like C 2-12 ⁇ -olefins; 1,4-endomethylenecyclohexene and like bicyclo-type monomers; methyl (meth)acrylate, ethyl(meth)acrylate and like (meth) acrylic acid esters; vinyl acetate, etc.
  • catalysts used for producing such polymers include not only generally used Ziegler-Natta catalysts, but also catalyst systems comprising a combination of a transition metal compound (e.g., a titanium halide such as titanium trichloride or titanium tetrachloride) supported on a support comprising, as a main component, magnesium chloride or like magnesium halide, with an alkylaluminum compound (such as tetraethylaluminum or diethylaluminum chloride), and further include metallocene catalysts.
  • a transition metal compound e.g., a titanium halide such as titanium trichloride or titanium tetrachloride
  • an alkylaluminum compound such as tetraethylaluminum or diethylaluminum chloride
  • melt flow rate (hereinafter referred to as “Mm”; measured according to JIS K 7210-1995) of the polyolefin-based resin used in the invention can be suitably selected according to the molding method to be employed, but it is recommended that the MR is usually 0.01 to 200 g/10 minutes, and preferably 0.05 to 100 g/10 minutes.
  • the polyolefin-based resin composition of the invention is obtainable by adding component (A), component (B), and, if necessary, an additive or additives as will be mentioned below in the item of “Other Additives” (for example, polyolefin resin modifiers, etc.) to a polyolefin-based resin.
  • the polyolefin-based resin composition of the invention may be produced by, for nipple, the following methods.
  • a method comprising providing a polyolefin-based resin (in powder, granule, flake, pellet, or other form), component (A), component (B), and if necessary, other additive(s), to give a desired composition ratio; and mixing (dry blending) the components using a conventional mixer (e.g., a Henschel mixer, ribbon blender, V blender, or the like) to yield a dry blended-type polyolefin-based resin composition.
  • a conventional mixer e.g., a Henschel mixer, ribbon blender, V blender, or the like
  • a conventional kneader such as a single screw or twin screw extruder
  • the method for making pellet-type polyolefin-based resin compositions includes a method using a high-concentration master batch containing 1 to 20 wt % (preferably 2 to 15 wt %) of component (A).
  • the high concentration master batch is diluted with an appropriate amount of a polyolefin-based resin to a desired composition ratio, and then the resulting composition is subjected to a molding processing.
  • the melt-kneading step described in the aforementioned item (ii) preferably comprises a step of dissolving component (A) completely in the melt of a polyolefin-based resin.
  • This step is important, particularly when the polyolefin-based resin composition of the invention is intended for the uses in which the transparency of the resulting molded articles is important.
  • the dissolution temperature can be determined, for example, as follows: First, a test polyolefin-based resin composition in the form of pellets is prepared. The test pellet thus prepared is then heated at a heating rate of 10° C./minute using a polarized light microscope equipped with a heating-stage. During the heating, the crystals of component (A) present in the pellet that is being heated is observed, and the temperature at which the crystals of component (A) have completely dissolved in the molten polyolefin-based resin is measured by visual observation.
  • provision of a process for preparing a polyolefin-based resin composition such as the process described in item (ii) above, also means provision of the following invention.
  • the present invention provides a method for improving the rigidity and transparency of a polyolefin-based resin, comprising adding to 100 weight parts of the polyolefin-based resin 0.01 to 1 weight part of component (A) and 0.005 to 1 weight part of component (B).
  • the present invention also provides a method for producing a polyolefin-based resin composition comprising 100 weight parts of the polyolefin-based resin, 0.01 to 1 weight part of component (A) and 0.005 to 1 weight part of component (B), the method comprising dissolving component (A) completely in a melt of the polyolefin-based resin.
  • the amount of component (A) according to the invention is 0.01 to 1 weight part, preferably 0.02 to 0.5 weight part, and more preferably 0.03 to 0.3 weight part, per 100 weight parts of a polyolefin-based resin.
  • the amount of component (B) according to the invention is 0.005 to 1 weight part, preferably 0.01 to 0.8 weight part, and particularly 0.02 to 0.5 weight part, per 100 weight parts of a polyolefin-based resin.
  • component (B) i.e., inorganic compound is used as filler in an amount as large as 5 to 30 weight parts per 100 weight parts of a polyolefin-based resin. It has been believed that fillers do not contribute to transparency. However, the present inventors have found a surprising effect that the use of a small amount of component (B) in combination with component (A) imparts even higher transparency. This effect was first discovered by the present inventors.
  • the ratio (by weight) of component (A) to component (B) is preferably 1:0.01-10, more preferably 1:0.05-5, more preferably 1:0.1-3, and particularly 1:0.1-2.
  • the effects of the invention will became even more significant by the addition of components (A) and (B) in the above ratio to a polyolefin-based resin.
  • the present invention provides a polyolefin-based resin nucleating agent composition.
  • component (A) and component (B) may be mixed beforehand (preferably uniformly), and added as a nucleating agent composition for the polyolefin-based resin.
  • the present invention provides a polyolefin-based resin nucleating agent composition comprising component (A) and component (B) as uniformly mixed.
  • the present invention also provides a polyolefin-based resin nucleating agent composition wherein component (A) and component (B) are present in such amounts that the weight ratio of component (A) to component (B) is preferably 1:0.01-10, more preferably 1:0.05-5, even more preferably 1:0.1-3, and particularly 1:0.1-2.
  • the nucleating agent composition of the present invention comprising component (A) and component (B) is in the form of a powder with good flowability, and is excellent in transferability through piping, and improves operation efficiency.
  • Examples of preferable methods for preparing the nucleating agent composition include dry blending, the method comprising using an organic solvent or like dispersion medium to mix the components uniformly, etc.
  • the polyolefin-based resin composition of the invention may comprise, in addition to components (A) and (B), “other additive(s)” such as polyolefin modifiers and the like according to its use or application, to the extent that the effects of the invention are not impaired.
  • polyolefin modifiers examples include various additives listed in “Tables of Positive Lists of Additives” edited by the Japan Hygienic Olefin and Styrene Plastics Association (January, 2002).
  • More specific examples include stabilizers (such as metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), UV absorbers (such as benzophenone compounds and benzotriazole compounds), antioxidants (such as phenol compounds, phosphorous ester compounds, and sulfur compounds), surfactants, lubricants (such as paraffins, waxes, and other aliphatic hydrocarbons, C 8-22 higher fatty acids, salts of metals (Al, Ca, Mg, Zn) with a C 8-22 higher fatty acid, C 8-22 higher aliphatic alcohols, polyglycols, esters of C 4-22 higher fatty acids with C 4-18 aliphatic monohydric alcohols, C 8-22 higher fatty acid amides, silicone oils, rosin derivatives), foaming agents, foaming auxiliaries, polymer additives, plasticizers (such as dialkyl phthalates and dialkyl hexahydrophthalates, etc.), crosslinking agents, crosslinking accelerators, antistatic agents, dis
  • the transparency of the polyolefin-based resin molded article of the invention tends to be further improved by adding any of the aforementioned higher fatty acid metal salts to the polyolefin-based resin composition of the invention.
  • C 8-22 higher fatty acid metal salts preferably calcium stearate, may be mentioned as such an additive.
  • Such additives are preferably used, per 100 weight parts of the polyolefin-based resin, in an amount of 0.001 to 0.2 weight part, and more preferably 0.005 to 0.1 weight part.
  • the polyolefin-based resin composition obtained as above is capable of yielding a useful polyolefin-based resin molded article exhibiting excellent crystallinity, heat resistance, rigidity and transparency.
  • the polyolefin-based resin molded article of the invention is obtained by molding the polyolefin-based resin composition of the invention according to a known molding process conventionally used in this field.
  • molding processes include injection molding, extrusion molding, blow molding, air-pressure forming, rotational molding, sheet molding, film molding, thermoforming, etc.
  • the process for molding the polyolefin-based resin composition of the invention preferably comprises molding the resin composition in which component (A) is completely dissolved in a melt of the polyolefin-based resin. This step is important, particularly when the polyolefin-based resin composition of the invention is intended for the uses in which the transparency of the resulting molded articles is important.
  • the molding temperature is generally from 160 to 300° C., preferably from 180 to 280° C., and more preferably from 200 to 260° C.
  • the polyolefin-based resin molded article of the invention thus obtained is excellent in crystallinity, transparency, rigidity and heat resistance. Hence, it can be similarly used in the fields in which polyolefin-based resin compositions comprising a nucleating agent such as metal phosphates, metal carboxylates, or benzylidene sorbitols have been used.
  • a nucleating agent such as metal phosphates, metal carboxylates, or benzylidene sorbitols have been used.
  • disposable syringes packaging materials for foods, plants, etc.
  • various cases such as cases for clothing, containers for storing clothing, etc.; cups for heat-packaging foods, packaging containers for retort-processed foods
  • containers and caps for seasonings such as miso, soy sauce, etc.
  • cases and containers for food stuff such as water, rice, bread, pickles, etc.
  • sundries such as cases for use in refrigerators, etc.; stationeries; electrical and mechanical parts; automobile parts, etc.
  • the polyolefin-based resin molded article of the invention has an advantage that, because amide-based compounds of component (A) themselves have excellent thermal stabilities, the article is substantially free from odor or taste transfer from the amide-based compound(s). Therefore, the molded article of the invention is especially useful for uses in which the prevention of odor or taste transfer is important (e.g., food packages, beverage bottles, cases for cosmetics, etc.).
  • pH values and particle size of inorganic compounds used in accordance with the invention were measured in the manner described below in items (1) and (2), respectively.
  • Polyolefin-based resin molded articles were evaluated for their crystallinity, rigidity, heat resistance and transparency in the manner described below in items (3) to (6), respectively.
  • the exothermic peak was determined in accordance with JIS-K-7121 using a differential scanning calorimeter (product name “Diamond DSC”, manufactured by Perkin Elmer, Inc.).
  • the peak temperature of the exothermic peak was defined as the crystallization temperature (° C.). The higher the crystallization temperature, the higher the crystallinity.
  • the crystallization rate increases with increasing crystallization temperature, and therefore high crystallization rate contributes to shortened molding cycle time in injection molding.
  • Flexural modulus was measured in accordance with JIS-K-7203 (1982) using an Instron universal tester (product name “Instron”, manufactured by Instron Japan Company Ltd.). Testing was conducted at a temperature of 25° C. and at a speed of 10 mm/min. The higher the flexural modulus, the higher the rigidity.
  • test pieces for measuring the flexural modulus had a length of 90 mm, a width of 10 mm and a height of 4 mm.
  • Deflection temperature (° C.) under load was measured in accordance with ASTM D648 using an HDT testing apparatus (product name “HDT TESTER 3M-2”, manufactured by Toyo Seiki Seisakusho, Ltd.). Testing was conducted at a flexural stress of 0.45 MPa using the edgewise method. The higher the deflection temperature under load, the superior the heat resistance.
  • test pieces for measuring the deflection temperature under load had a length of 110 mm, a width of 13 mm and a height of 40 mm.
  • the haze value (%, 1-mm thickness) was measured in accordance with ASTM D1003 using a haze meter (product name “Haze-gard II”, manufactured by Toyo Seiki Seisakusho, Ltd.). The lower the value, the higher the transparency.
  • the dried product was pulverized in a mortar, and passed through a standard sieve having openings of 106 ⁇ m (in accordance with JIS-Z-8801 standard) to afford 18.8 g of 1,2,3-propanetricarboxylic acid tri(2-methylcyclohexylamide) (hereinafter abbreviated to “PTC-2MeCHA”) in accordance with the invention (yield: 74%).
  • component (A) i.e., PTC-2MeCHA prepared in Preparation Example 1
  • component (B) Hydrotalcite 1 (i.e., Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O, product name “DHT-4A”, manufactured by Kyowa Chamical Industry Co., Ltd.)
  • additives i.e., 0.05 weight part of tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane (product name “IRGANOX 1010”, manufactured by Ciba Specialty Chemicals Inc.) and 0.05 weight part of tetrakis(2,4-di-t-buthylphenyl)phosphite (product name “IRGAFOS 168”, manufactured by Cib
  • the dry-blended type polyolefin-based resin composition was then melt-kneaded with a 20-mm diameter single-screw extruder at a resin temperature of 240° C.
  • the extruded strands were cooled with water, and then cut to yield a pellet-type polyolefin-based resin composition in accordance with the invention.
  • the pellets thus obtained were subsequently injection molded at a resin temperature of 250° C. and a mold temperature of 40° C. to yield a polyolefin-based resin molded article (test piece) in accordance with the invention.
  • the crystallization temperature, flexural modulus, deflection temperature under load and haze value of the test piece, along with the pH value and particle size of the inorganic compound used were measured. The results are presented in Table 1.
  • Example 1 The procedure of Example 1 was repeated, except that the type or the amount of component (A) or component (B) were changed to those listed in Table 1, thus giving polyolefin-based resin molded articles (test pieces) in accordance with the invention.
  • Example 1 The procedure of Example 1 was repeated, except that the type or the amount of component (A) and component (B) were changed to those listed in Table 3, thus obtaining a polyolefin-based resin molded article (test piece) not in accordance with the invention.
  • the crystallization temperature, flexural modulus, deflection temperature under load, and haze value of the test piece, along with the pH value and particle size of the inorganic compound used were measured. The results are presented in Table 3. Note that activated clay is listed in Table 3 as in the column labeled “component (B)”; however, it is different from component (B).
  • Type Type (wt parts) Type (wt parts) pH ( ⁇ m) (° C.) (MPa) (° C.) (%)
  • Type Type (wt parts) Type (wt parts) pH ( ⁇ m) (° C.) (MPa) (° C.) (%)
  • “Hydrotalcite 1” is Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O, product name “DHT-4A”, manufactured by Kyowa Chemical Industry Co., Ltd;
  • “Hydrotalcite 2” is Mg 4.5 Al 2 (OH) 13 CO 3 , product name “DHT-4A2”, manufactured by Kyowa Chemical Industry Co., Ltd;
  • Lithium aluminium double hydroxide is LiAl 4.5 (OH) 12 CO 3 .3H 2 O, product name “Mizukalac L”, manufactured by Mizusawa Industrial Chemicals, Ltd;
  • “Hydrotalcite 3” is Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O, product name “DHT-6”, manufactured by Kyowa Chemical Industry Co., Ltd.;
  • Talc is Mg 3 Si 4 O 10 (OH) 2 , product name, “Micro Ace P-6”, manufactured by Nippon Talc Co., Ltd; and
  • Mg (OH) 2 is product name “Magsarat F”, manufactured by Kyowa Chemical Industry Co., Ltd.
  • b-PP polypropylene block copolymer having an ethylene content of 9.5 wt. %
  • b-PP polypropylene block copolymer having an ethylene content of 9.5 wt. %
  • Example 14 The procedure of Example 14 was repeated, except that the type of component (B) was changed as listed in Table 4, thus producing a polyolefin-based resin molded article (test piece) in accordance with the invention.
  • the crystallization temperature, flexural modulus and deflection temperature under load of the test piece, along with the pH value and particle size of the inorganic compound used were measured. The results are presented in Table 4.
  • Example 14 The procedure of Example 14 was repeated, except that the type or the amount of component (A) or component (B) were changed to those listed in Table 4, thus producing a polyolefin-based resin molded article (test piece) not in accordance with the invention.
  • the crystallization temperature, flexural modulus and deflection temperature under load of the test piece were measured. The results are presented in Table 4.
  • Crystalli- Polyolefin-based resin molded article Crystalli- Polyolefin- Component (A): zation Flexural Deflection based amide-based compound Component (B): inorganic compound temper- mod- temperature resin Amount Amount Particle size ature ulus under load Type Type (wt parts) Type (wt part) pH ( ⁇ m) (° C.) (MPa) (° C.) Ex. 14 b-PP PTC-2MeCHA 0.15 Hydrotalcite 1 0.05 8.6 0.43 129 1280 104 Mg 4.5 Al 2 (OH) 13 CO 3 •3.5H 2 O Ex.
  • r-PP polypropylene random copolymer having an ethylene content of 3.0 wt. %
  • Example 16 The procedure of Example 16 was repeated, except that the type or the amount of component (A) or component (B) was changed as shown in Table 5, thus giving a polyolefin-based resin molded article (test piece) not in accordance with the invention.
  • a polyolefin-based resin composition in accordance with the invention is suitable for use in known molding processes such as injection molding, film-molding, blow molding, extrusion molding, thermoforming, etc.
  • a resin-molded article obtained by molding such a polyolefin-based resin composition exhibits excellent crystallinity, rigidity, heat resistance and transparency, and therefore used as a material for medical instruments, packaging materials for foods, plants, etc., cases for a variety of uses, packaging containers for foods, containers for use in microwave ovens, sundries, stationeries, electrical and mechanical parts, automobile parts, etc.
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WO2012112542A1 (en) * 2011-02-14 2012-08-23 Mayzo, Inc. Supported crystal nucleating agent for polypropylene
EP2639266A1 (en) * 2010-11-10 2013-09-18 Adeka Corporation Polypropylene resin composition
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US11667603B2 (en) 2019-12-12 2023-06-06 Milliken & Company Trisamide compounds and compositions comprising the same
US11724983B2 (en) 2019-12-12 2023-08-15 Milliken & Company Trisamide compounds and compositions comprising the same
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US9023921B2 (en) 2009-05-13 2015-05-05 New Japan Chemical Co., Ltd. Method for inhibiting crystal growth rate of amide compound and method for producing molded article of polyolefin-based resin
WO2012045288A1 (en) * 2010-10-05 2012-04-12 Polymer Institute Brno, Spol. S R.O. : method of preparation of nucleated semi-crystalline polymer
US9062184B2 (en) 2010-10-05 2015-06-23 Polymer Institute Brno, Spol. S.R.O. Method of preparation of nucleated semi-crystalline polymer
EP2639266A1 (en) * 2010-11-10 2013-09-18 Adeka Corporation Polypropylene resin composition
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WO2012112542A1 (en) * 2011-02-14 2012-08-23 Mayzo, Inc. Supported crystal nucleating agent for polypropylene
US11667603B2 (en) 2019-12-12 2023-06-06 Milliken & Company Trisamide compounds and compositions comprising the same
US11724983B2 (en) 2019-12-12 2023-08-15 Milliken & Company Trisamide compounds and compositions comprising the same
US11773054B2 (en) 2020-12-14 2023-10-03 Milliken & Company Trisamide compounds and compositions comprising the same

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